Certain polyepoxide treated amine modified thermoplastic phenol-aldehyde resins and method of making same



United States Patent CERTAIN POLYEPOXIDE TREATED AMINE MODI- FIED THERMOPLASTIC PHENQL-ALDEHYDE RESINS AND METHOD F MAKING SAME Melvin De Groote, St. Louis, and Kwan-Ting Sheri, Brentwood, Mo., assignors to Petrolite Corporation, Witmington, 'Del., a corporation of Delaware No Drawing. Original application February 24, 1953,

Serial No. 338,577. Divided and this application May 1, 1956, Serial No. 582,045

14 Claims. (Cl. 26053) 2,828,282 Patented Mar. 25, 1958 of connecting bridges, i. e., divalent linking radicals. Our

ture of polymer and monomer.

Stated another way we would prefer to use. materials of the kind described, for example, in U. S. Patent No. 2,530,353, dated November 4, 1950. Said patent describes compounds having the general formula The present invention is a continuation-in-part of our 5 co-pending application, Serial No. 305,079, filed August 18, 1952, now abandoned, and a division of our co- GET-'0 pending application Serial No. 338,577, filed February 24, O 2

1953, Patent No. 2,771,439.

Our invention is concerned with new chemical products Wherem R 13 ahphatlc hydrocarbon bridge each n or compounds useful as demulsifying agents in processes or procedures particularly adapted for preventing, breaking or resolving emulsions of the water-in-oil type and particularly petroleum emulsions. Our invention is also dependently has one of the values 0 and l, and X is an alkyl radical containing from 1 to 4 carbon atoms.

The list of patents hereinafter referred to in the text as far as polyepoxide goes, is as follows:

concerned with the application of such chemical products or compounds in various other arts and lndustnes as well Patent Dated Inventor as with methods of manufacturing the new'chemrcal products or compounds which are of outstanding val e in 2,122,958 July 5,1938 Schafer. d l ifi fl JgDeefmlaer 123, 1938. Miklejska et al.

The products of our invention are obtained by the j 225 81, method of first condensing certam phenol-aldehyde resins, ggg e l i e t a l. hereinafter describgd inbdzeitaihdwith1 certiaifn cycllilcham- 5 1 37, 594i 1 611, -s e ein fte' escri e in etai an rrn de 1 1 1118 Y 42 Fimm et 9 h r a f n d b i e 2,331,448.. October 12, 1943 Winning et al. which condensation 1s 0 owe y reactlon of e resm 2,430,002 De Groom condensate with certain phenolic polyepoxldes, also here- 35 2-457329- December 1948M" Swem aL 2,462,047. February 15, 1949 lnafter described in detail, and cogenencally associated 2,462,048. "do D l 2,482,748. September 27, 1949 Dietzler. compounds folmed 1n the preparat10n of the polyepoxldes 2,488,134 November 15, 1mm Mikeska et al- In preparing dlepoxldes or the low molal polymers ,2 2,522.- fipriliiltliggd giegzzle' elt a1.

P oeea. one does usually obtam cogenenc matenals which may 2,506,486 May 27 1950 Bender et aL include H1OI106pOX1d6S. However, the cogenenc nnxture 2,515,906 July 18, 1950 Stevens et a1. is mvarrably charactenzed by the fact that there 1s on 322%; --gg--- 38- the average, based on the molecular weight of course, 312%??? loI ibe 1111195 0555 firemen v c4" 0V8l11 er avens.

more than *P group Per i 2,564,191..- August 14. 1951 De Groote et al A more l1m1ted aspect of the 1nvent1on 1s repre- 2,575, November 20,1951 Newey et a1 sented by the reaction product of (A) an amine-modig gg'fi i? 8,1901" fig fied' phenol-aldehyde resin condensate as described, and 2,582,985 Maryann: I: Granite. (B) a member of the class of (1) compounds of the following formula Y The compounds having two oxlrane mugs and employed for comblnatlon with the reactive amine-modified phenoland (2) cogenerically associated compounds formed in the preparation of (l) preceding.

It so happens that the bulk of information concerned with the preparation of compounds having two oxirane rings appears in the patent literature and for the most aldehyde resin condensates as herein described. are compounds of the following formula and, cogenerically assoclated compounds formed in their preparation:

in which R represents a divalent radical selected from the class of ketone residues formed by the elimination of the ketonic oxygen atom and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical the divalent radical, the divalent sulfone radical, and the divalent monosulfide radical A-, the divalent radical and the divalent disulfide radical SS-; and R is inwhich R, R and R represent a member of the class of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; n represents an integer selected from the class. of zero and 1, and n represents a whole number not greater than 3. The above mentioned compounds and those cogenerically associated compounds formed in their preparation are thermoplastic and organic solvent-soluble; Reference to being thermoplastic characterizes them as being liquids at ordinary temperature or readily convertible to liquids by merely heating below the point of pyrolysis and thus differentiates them from infusible resins. Reference to being soluble in an organic solvent means any of the usual organic solvents, such as important because the instant invention is directed towards products which are not insoluble resins and have certain solubility characteristics not inherent in the usual thermosetting resins. Note, for example, that said U. S. Patent No. 2,494,295 describes products wherein the epoxide derivative can combine with a sulfonamide resin. The intention in said U. S. Patent 2,494,295, of course, is to obtain ultimately a suitable resinous product having the characteristic of a comparatively insoluble resin.

Having obtained a reactant having generally 2 epoxy rings as depicted in the last formula preceding, or low molal polymers thereof, it becomes obvious the reaction can take place with any amine-modified phenol-aldehyde resin by virtue of the fact that there are always present reactive hydroxyl groups which are part of the phenolic nuclei and there may be present reactive hydrogen atoms attached to a nitrogen atom, or an oxygen atom, depending on the presence of a hydroxylated group or seconda'ry amino group.

To illustrate the products which represent the subject matter of the present invention reference will be made to a reaction involving a mole of the oxyalkylating agent, i. e., the compound having two oxirane rings and triethanolamine. Proceeding with the example previously described it is obvious the reaction ratio of two moles of the amine condensate to one mole of the oxyalkylating agent gives a product which may be indicated as follows:

(condensate) alcohols, ketones, esters, ethers, mixed solvents, etc. Reference to solubility is merely to differentiate from a reactant which is not soluble and might be not only insoluble but also infusible. Furthermore, solubility is a factor insofar that it is sometimes desirable to dilute the compound containing the epoxy rings before reacting with amine. In such instances, of course, the solvent selected would have to be one which is not susceptible to oxyalkylation, as for example, kerosene, benzene, toluene, dioxane, various ketones, chlorinated solvents, dibutyl ether, dihexyl ether, ethyleneglycol diethylether, diethyleneglycol diethylether, and dimethoxytetraethyleneglycol.

The expression epoxy is not usually limited to the 1,2- epoxy ring. The 1,2-epoxy ring is sometimes referred to as the oxirane ring to distinguish it from other epoxy rings. Hereinafter the word epoxy unless indicated otherwise, will be used to mean the oxirane ring, i. e., the 1,2-epoxy ring. Furthermore, where a compound has two or more oxirane rings they will be referred to as polyepoxides. They usually represent, of course, 1,2- epoxide rings or oxirane rings in the alpha-omega position. This is a departure, of course, from the standpoint of strictly formal nomenclature as in the example of the simplest diepoxide which contains at least 4 carban atoms and is formally described as l,2-epoxy-3,4-epoxybutane (1,2-3,4 diepoxybutane).

It well may be that even though the previously suggested formula represents the principal component, or

I components, of the resultant or reaction product described in the previous text, it may be important to note that somewhat similar compounds, generally of much higher molecular weight, have been described as complex resinous epoxides which are polyether derivatives of polyhydric phenols containing an average of more than one epoxide group per molecule and free from functional groups other than epoxide and hydroxyl groups. See U. S. Patent No. 2,494,295, dated January 10, 1950, to Greenlee. The compounds here included are limited to the monomers or the low molal members of such series and generally contain two epoxide rings per molecule and may be entirely free from a hydroxyl group. This is Gross.

(condensate) inwhich the various characters have their previous signiticance and the characterization condensate is simply an abbreviation for the condensate which is described in greater detail subsequently.

Such final product in turn also must be soluble but solubility is not limited to an organic solvent but may include water, or for that matter, a solution of water containing an acid such as hydrochloric acid, acetic acid, hydroxyacetic acid, etc. In other words, the nitrogen groups present, whether two or more, may or may not be significantly basic and it is immaterial whether aquesolubility represents an anhydro base or the free base (combination with water) or a salt form such as the acetate, chloride, etc. The purpose in this instance is to differentiate from insoluble resinous materials, particularly those resulting from gelation or cross-linking. Not only does this property serve to dilferentiate from instances where an insoluble material is desired, but also serves to emphasize the fact that in many instances the preferred compounds have distinct water-solubility or are distinctly dispersible in 5% gluconic acid. For instance, the products freed from any solvent can be shaken with 5 to 20 times their weight of 5% distilled Water at ordinary temperature and show at least some tendency towards being self-dispersing. The solvent which is generally tried is xylene. If xylene alone does not serve then a mixture of xylene and methanol, for instance, parts of xylene and 20 parts of methanol, or 70 parts of xylene and 30 parts of methanol, can be used. Sometimes it is desirable to add a small amount of acetone to the xylene-methanol mixture, for instance, 5% to 10% of acetone.

The polyepoxide-treated condensates obtained in the manner described are, in turn, oxyalkylation-susceptible and valuable'derivatives can be obtained by further reaction with ethylene oxide, propylene oxide, ethylene imine, etc.

Similarly, the polyepoxide-derived compounds can be reacted with a product having both a nitrogen group and a 1,-2-epoxy group, such as 3-dialkylaminoepoxypropane. See U. S. Patentldo. 2,520,093, dated August 22, 1950, to

Although the herein described products have a number of industrial applications, they are of particular value for resolving petroleum emulsions of the water-in-oil type that are commonly referred to as cut oil, roily oil, emulsified oil, etc., and which comprises fine droplets of naturally-occurring waters or brines dispersed in a more or less permanent state throughout the oil which constitutes the continuous phase of the emulsion.

The new products are useful as wetting, detergent and leveling agents in the laundry, textile and dyeing industries; as wetting agents and detergents in the acid washing of building stone and, brick; as wetting agents and spreaders in the application of asphalt in road building and the like; as a flotation reagent in the flotation separation of various aqueous suspensions containing negatively charged particles, such as sewage, coal Washing waste water, and various trade wastes and the like; as germicides, insecticides, emulsifying agents, as, for example, for cosmetics, spray oils, water-repellent textile finishes; as lubricants, etc.

As far as the use of the herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in the form of the free base or hydrate, i. e., combination with water or particularly in the form of a low molal organic acid salt such as the gluconates or the acetate or hydroxy acetate, have sufficiently hydrophile character to at least meet the test set forth in U. S. Patent No. 2,499,368, dated March 7, 1950, to De Groote et al. In said patent such test for emulsification using a waterinsoluble solvent, generally xylene, is described as an index of surface activity.

In the present instance the various condensation products as such or in the form of the free base or in the form of the acetate, may not necessarily be xylene-soluble although they are in many instances. If such compounds are not xylene-soluble the obvious chemical equivalent or equivalent chemical test can be made by simply using some suitable solvent, preferably a Water-soluble solvent such as ethylene glycol diethylether, or a low molal alcohol, or a mixture to dissolve the appropriate product being examined and then mix with the equal weight of xylene, followed by addition of water. Such test is obviously the same for the reason that there will be two phases on vigorous shaking and surface activity makes its presence manifest. It is understood the reference in the hereto appended claims as to the use of xylene in the emulsification test includes such obvious variant.

For purpose of convenience what is said hereinafter will be divided into nine parts with Part 3, in turn, being divided into three subdivisions:

Part 1 is concerned with our preference in regard to the polyepoxide and particularly the diepoxide reactant;

.Part 2 is concerned with certain theoretical aspects of diepoxide preparation;

Part 3, Subdivision A, is concerned with the preparation of monomeric diepoxide, including Table I;

Part 3, Subdivision B, is concerned with the preparation of low molal polymeric epoxides or mixtures containing low molal polymeric epoxides as well as the monomer and includes Table II;

Part 3, Subdivision C, is concerned with miscellaneous phenolic reactants suitable for diepoxide preparation;

Part 4 is concerned with the phenol-aldehyde resin which is subjectedto modification by condensation reaction to yield the amine-modified resin;

Part 5 is concerned with appropriate basic cyclic amidines which may be employed in the preparation of the herein-described amine-modified resins;

Part 6 is concerned with reactions involving the resin, the amine, and formaldehyde to produce specific products or compounds which are then subjected to reaction with polyepom'des;

Part 7 is concerned with the reactions involving the two preceding types of materials and examples obtained by such reaction. Generally speaking, this involves notha 6 ing more than a reaction between 2 moles of a previously prepared amine-modified phenol-aldehyde resin condensate as described, and one mole of a polyepoxide so as to yield a new and larger resin molecule, or comparable product;

Part 8 is concerned with the resolution of petroleum emulsions of the water-in-oil type by means of the previously described chemical compounds or reaction products; and

Part 9 is concerned with uses for the products herein described, either as such or after modification, including any applications other than those involving resolution of. petroleum emulsions of the water-in-oil type.

PART 1 As will be pointed out subsequently, the preparation of polyepoxides may include the formation of a small amount of material having more than two epoxide groups per molecule. If such compounds are formed they are perfectly suitable except to the extent they may tend to produce ultimate reaction products which are not solventsoluble liquids or low-melting solids; Indeed, they tend to form thermosetting resins or insoluble materials. Thus, the specific objective by and large is to produce diepoxides as free as possible from any m-onoepoxides and as free as possible from polyepoxides in which there are more than two epoxide groups per molecule. Thus, for practical purposes what is said hereinafter is largely limited to polyepoxides in the form of diepoxides.

As has been pointed out previously one of the reactants.

employed is a diepoxide reactant. It is generally obtained from phenol (hydroxybenzene) or substituted phenol. The ordinary or conventional manufacture of the epoxides usually results in the formation of a co-generic mixture as explained subsequently. Preparation of the monomer or separation of the monomer from the remaining mass of the co-generic mixture is usually expensive. If monomers were available commercially at a low cost, or if they,

could be prepared without added expense for separation, our preference would be to use the monomer. Certain monomers have been prepared and described in the literature and will be referred to subsequently. However, from :a practical standpoint one must weigh the advantage, if any, that the monomer has over other low molal polymers from a cost standpoint; thus, we have found that one might as well attempt to prepare a monomer and fully recognize that there may be present, and probably invariably are present, other low molal polymers in comparatively small amounts. Thus, the materials which are most apt to be used for practical reasons are either monomers with some small amounts of polymers present or mixtures which have a substantial amount of polymers present. Indeed, the mixture can be prepared free from monomers and still be satisfactory. Briefly, then, our preference is to use the monomer or the monomer with the minimum amount of higher polymers.

It has been pointed out previously that the phenolic nuclei in the epoxide reactant may be directly united, or united through a variety of divalent radicals. Actually, it is our preference to use those which are commerically available and for most practical purposes it means instances where the phenolic nuclei are either united directly without any intervening linking radical, or else united by a ketone residue or formaldehyde residue. The commercial bis-phenols available now in the open market illustrate one class. The diphenyl derivatives illustrate a second class, and the materials obtained by reacting substituted monofunctional phenols with an aldehyde illustrate the third class. may be used but our preference rests with these classes due to their availability and ease of preparation, and also due to the fact that the cost is lower than in other examples.

Although the diepoxide reactants can be produced inmore than one way, as pointed out elsewhere, our pref- All the various known classes erence is to produce them by, means of the epichlorohydrin reaction referred to in detail subsequently.

One epoxide which can be purchased in the open market and contains only a modest amount of polymers corresponds to the derivative of bis-phenol A. It can be used as such, or the monomer can be separated byan added step which involves additional expense. This compound of the following structure is preferred as the epoxide reactant and will be used for illustration repeatedly with the full understanding that any of the other epoxides described are equally satisfactory, or that the higher polymers are satisfactory, or that mixtures of the monomer and higher polymers .are satisfactory. The formula for this compound is Referrence has just been made to bis-phenol A and a suitable epoxide derived therefrom. Bis-phenol A is dihydroxy-diphenyl-dimethyl methane, with 4,4 isomers predominating and with lesser quantities of the 2,2 and 4,2 isomers being present. It is immaterial which one of these isomers is used and the commercially available mixture is entirely satisfactory.

Attention is again directed to the fact that in the instant part, to wit, Part 1, and in succeeding parts, the text is concerned almost entirely with epoxides in which there is no bridging radical or the bridging radical is derived from an aldehyde or a ketone. It would be immaterial if the divalent linking radical would be derived from the other groups illustrated for the reason that nothing more than mere substitution of one compound for the other would be required. Thus, what is said hereinafter, although directed to one class or a few classes, applies with equal force and efit'ect to the other classes of epoxide reactants.

If sulfur-containing compounds are prepared they should be freed from impurities with considerable care for the reason that any time that a low-molal sulfur-containing compound can react with epichlorohydrin there may be formed a by-product in which the chlorine happened to be particularly reactive and may represent a product, or a mixture of products, which would be unusually toxic, even though in comparatively small concentration.

PART 2 Treatment with epichlorohydrin, for example, does not yield this product initially but there is an intermediate produced which can be indicated by the following structure:

Treatment with alkali, of course, forms the epoxy ring.

A number of problems are involved in attempting to produce this compound free from cogeneric materials of related composition. The difficulty stems from a number of sources and a few of the more important ones are as follows:

' (1) Theclosing of the epoxy ring involves the use of caustic soda or the like which, in turn, is an effective catalyst in causing the ring to open in an oxyalkylation reaction.

Actually, what may happen for any one of a number of reasons is that one obtains a product in which there is only one epoxide ring and there may, as a matter of fact, be more than one hydroxyl radical as illustrated by the following compounds:

CH3 'H H H I H H H HC-Cg0 O'I(|J?H \O/ OH; OH C1 CH3 H H' H H H H w ti ar-r 0 OH: OH on (2) Even .if one starts with the reactants in the preferred ratio, to wit, two parts of epichlorohydrin to one part of bis-phenol A, they do not necessarily so react and as a result one may obtain products in which more than two epichlorohydrin residues become attached to a single bis-phenol A nucleus by virtue of the reactive hydroxyls present which enter into oxyalkylation reactions rather than ring closure reactions.

(3) As is well known, ethylene oxide in the presence of alkali, and for that matter in the complete absence of water, forms cyclic polymers. Indeed, ethylene oxide can produce a solid polymer. This same reaction can, and at times apparently does, take place in connection with compounds having one, or in the present instance, two substituted oxirane rings, i. e., substituted 1,2 epoxy rings. Thus, in many ways it is easier to'produce a polymer, particularly a mixture of the monomer, dimer and trimer, than it is to produce the monomer alone. p

(4) As has been pointed out previously, monoepoxides may be present and, indeed, are almost invariably and inevitably present when one attempts to produce polyepoxides, and particularly diepoxides. The reason is the one which has been indicated previously, together with the fact that in the ordinary course of reaction a diepoxide, such as may react with a mole of bis-phenol A to give a monoepoxy structure. Indeed, in the subsequent text immediately following reference is made to the dimers, trimers and tetramers in which two epoxide groups are present. Needless to say, compounds can be .formed which correspond in every respect except that one terminal epoxide group is absent and in its place is a group having one chlorine atom and one hydroxyl group, or else two hydroxyl groups, or an unreacted phenolic ring.

(5) Some reference has been made to the presence of a chlorine atom and although all effort is directed towards the elimination of any chlorine-containing molecule yet it is apparent that this is often an ideal approach rather than a practical possibility. Indeed, the same sort of reactants are sometimes employed to obtain products in which intentionally there is both an epoxide group and a chlorine atom present. See U. S. Patent No. 2,581,464, dated January 8, 1952, to Zech.

What has been said in regard to the theoretical aspect is, of course, closely related to the actual method of preparation which is discussed in greater. detail in Part 3, particularly subdivisions A and B. There can be no clear line between the theoretical aspect and actual preparative steps. However, in order to summarize or illustrate what has been said in Part 1, immediately preced-' ing reference will be made to a typical example which 211- ready has been employed for purpose of illustration. The wit, compounds having both an epoxy ring or the equivparticular example is g alent and also a hydroxyl group, one need go no further CH than to consider the reaction product of 3 H H H I H H CH3 Hoo-oooO0-o-o--0H 5 n H n 1 H H H H I H HO---CCO OOC-C-OH CH3 0 \0/ H 1 n \0/ 3 It g fz i 5 .3%? 2: 2 mammal combme and bisphenol A in a mole-for-rnole ratio, since the initial ma 1 y W one o e o reactant would yield a product having an unreacted CH3 epoxy ring and two reactive hydroxyl radicals. Refer- O QG ring again to a previous formula, consider an example 1 where two moles of bisphenol A have been reacted with 3 3 moles of epichlorohydrin. The simplest compound to produce the product which is one step further along, formed would be thus:

' (1H5 15 1H, 5 l 1 CH2 H3 CH3 H2 8 11 I/ l I CH2 CH at least, towards polymerization. In other words, one Such a compound is comparable to other compounds prior example shows the reaction product obtained from having both the hydroxyl and epoxy ring such as one mole of the bisphenol A and tWO m s of P 9,10-epoxy octadecanol. The ease with which this type of y Thls Product In tum would fehfesent moles compound polymerizes is pointed out by U. S. Patent No. of blsphenol A and four moles of eplchlorohydrln. 2,457,329, dated December 28, 1948, to Swern et al.

For purpose of brevity, without going any further, the next formula is in essence one which, perhaps in an bis the moi'no resin p rfilii c t ai sil ablg nllet ihe nam sof Eiaf Resi ns as n23; and a ltydroxyl radical Illustrated by compounds sold in the open market. .See, also, chemical pamphlet W Instead of the oxlrane T1113 P Y ring) there entitled Epon Surface-Coating Resins, Shell Chemical 15 Presant a 9 3 ring- Such compounds are dfifiva- Corporation, New York City. The word Epon is a" tives of trimethylene oxide rather than ethylene oxide. registered trademark of the Shell Chemical Corporation. See U. S. Patents Nos. 2,462,047 and 2,462,048, both The same difficulty which involves the tendency to polymerize on the part of compounds having a reactive ring CH3 (IJH CH5 I H: CH: n' CH3 CH2 05 (JH a For the purpose of the instant invention, n may repdated February 15, 1949, to Wyler. resenta number including zero, and at the most a low At the expense of repetition of what appeared previnumber such as l, 2 or 3. This limitation does not exist ously, it may be well to recall that these materials may in actual efforts to obtain reslns as differentiated from vary from simple soluble non-resinous to complex nonthe herein described soluble materials. It is quite probsoluble resinous epoxides which are polyether derivatives able that in the resinous products as marketed for coatof polyhydric phenols containing an average of more ing use the value of n' is usually substantially higher. than one epoxide group per molecule and free from func- Note again what has been said previously that any fortional groups other than epoxide and hydroxyl groups. mula is, at best, an over-simplification, or at the most rep- The former are here included, but the latter, i. e., highly resents perhaps only the more important or principal resinous or insoluble types, are not. constituent or constituents. These materials may vary In summary then in light of what has been said, comfrom simple non-resinous to complex resinous epoxides pounds suitable for reaction with amines may be sumwhich are polyether derivatives of polyhydric phenols conmarized by the following formula:

taining an average of more than one epoxide group per or for greater simplicity the formula could be restated molecule and free from functional groups other than thus:

epoxide and hydroxyl groups. in which the various characters have their prior signifi- Referrmg now to what has been said previously, to cance and in which R 0 is the divalent radical obtained by the elimination of a hydroxyl hydrogen atom and a nuclear hydrogen atom from the phenol ethers, have been described in a number of patents. For convenience, reference Will be made to two only, to Wit, aforementioned U. S. Patent 2,506,486, and aforementioned U. S. Patent No. 2,530,353.

Purely by way of illustration, the following diepoxides, or diglycidyl ethers as they are sometimes termed, are included for purpose of illustration. These particular compounds are described in the two patents just mentioned.

TABLE I Ex- Patent ample Diphenol Diglyeidyl ether refernumber ence CH2(CBHLOH)Z Dl(epoxypropoxyphenyl)methane 2,506,486 CH3CH(OGH4OH)2- Di(epoxypropoxyphenyl)methylmethane 2,506, 6 011920 C@Hi0H)r Di(epoxypropoxyphenyl)dimethylrnethane 2, 506, 486 2 5O( H3)(O6H4OH)2 Di(epoxypropoxyphenybethylmethylmethane 2, 506,486 (C2H5)20(OBH4OH)2 Di(epoxypropoxyphenyl)diethylmethane 2, 566, 486 CH3O(C3H1)(C@H4OH)2 Di(epoxypropoxyphenyl)methylpropylrnethane 2, 506,486 CIIBC(C5H5)(CBHAOH)2 Di(epoxypropoxyphenyl)methylphenylmethane 2, 506,486 CzH C(CsH )(GeH-i0H): Dl(epoxypr0poxyphenyl)ethylphenylmethane. 2, 506,486 CzH1 tH5)( sH4OH)z Di(epoxypropoxyphenyl)propylphenylmethane 2, 506,486 C4119 (C5H5)(C5H40H)2- Di(epoxypropoxyphenyl)butylphenylmethane. 2, 566,486 (CH3C6H4)CH(O$H4 11):. Di(epoxypropoxyphenyl)tolylmethane t. 2, 506,486 (QH3CGH4)C (OHQ)(OBH4OH)- Di(epoxypropoxyphenyl)tolylmethylmethane 2, 506,486 Dihydroxy diphenyl 4,4-b1s(2,3-epoxypropoxy)diphenyl 2,530,353 (011;) C(OiH5.CuH3OH)n 2,2-bis(4-(2,3-epoxypr0poxy)Z-tertiarybutyl phenyl)pr0pane 2, 530, 353

class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; n represents an integer selected from the class of zero and 1, and n represents a Whole number not greater than 3.

PART 3 Subdivision A The preparations of the diepoxy derivatives of the diphenols, which are sometimes referred to as diglycidyl Subdivision B TABLE II l C OC O R1[R],,-R 0-C-CC OR1[R],.R1O-CC-C H: H H: H: J) H2 H: H H2 (in which the characters have their previous significance) Example R1O from HR 0H P 'n i n Remarks number B1 Hydroxy benzene CH; 1 0,1,2 Phenol known as bis-phenol A. Low polymeric mixture about 3:; or more where 'n=0, remainder largely where n=l, some where n=2. CH3

B2 do CH: 1 0, l, 2 Phenol known as bis-phenol B. See note ([1 regarding Bl above. l CH: Ha

B3 Orthobutylphenol CH; 1 0, 1,2 Even though n is preferably 0, yet the usual reaction product might well con- --C tain materials where n is 1, or to a l lesser degree 2. CH: 7

B4 Orthoamylphenol (1111 1 0,1,2 Do.

. B5. Orthooctylphenol EH: 1 0,1,2 Do.

I CH:

B6 Orthononylphenol (EH; 1 0,1,2 Do. PLF

TABLE II-Continued Example R1Ofrom HR H R n 'n' Remarks number B7 orthododecylphenol CH1 1 0,1,2 Even though '17, is preferably 0, yet the usual reaction product m1ght well con- O- tain materials where n is 1, or to a lesser degree 2. H1

B8 Metacresol CH 1 0 1 2 See prior note. This phenol used as initial materiallsknown asbis-phenol '-C O. For other suitable bis-phenols see I U. 8. Patent 2,564,191. CH: B9 do .1-- CH1 1 0,1, 2 See prior note.

1310 Dlbutyl(ortho-pare)phei1ol. 1(E 1 0,1,2 Do.

B11 Diamyl(ortho-para) phenol- %I 1 0,1,2 Do.

I H B12 Dioctyl (ortho-para) phenoll 1 0,1,2 Do.

B13 Dinonyl(ortho-para)phenol. l[ 1 0,1,2 Do.

B14.... Diamyl (ortho-para) phenol. E l 1 0,1,2 Do.

1315-.---. -..--do -1. 1g 1 0,1,2 Do.

B Hydroxy benzene 0 1 0,1,2 Do.

B17 Diamyl phenol (ortho-para). -S'--S 1 0,1,2 Do. ma an -s- '1 0,1,2 D

B19 Dlbntylphenol(ortho-para).. 1l}i 1g; 1 0,1,2 Do.

"R20 rln H H 1 0,1,2 Do.

B21 Dlnonyl phienol(6rtho-para). 1g '1g 1 0,1,2 Do.

1322 Hydroxy benzene O 1 0,1,2 Do.

B23 N 0 0,1,2 Do. B24 0rtho-isopropyl phenol CH; 1 0,1,2 Seepriornote. (As topreparation 014,4

isopropylidene bis-(2-isopropylphenol)- see U. 8. Patent No. 2,482,748, dated (jJH Sept. 27, 1949, to Dietzler.)

B25 Pare-0e l henol.-.- -VCH S-OH '1 0 1,2 See prior note. (As to preparation of the w p r- 1 v phenol sulfide see U. 1?. Patent No.

2,488,134, dated Nov. 15, 1949, to

Mikeska et al.) 1

B26 Hydro'xybenzene CH1 1 0,1,2 See prior note. (As to preparation of the phenol sulfide see U. 8; Patent N o. 2,526,546.)

Subdivision C in converting di'p'henyl into a diglycidyl e'ther regardless of the nature of the bond between the two phenolic nuclei.

For purpose of illustration attention is directed to numer- Tlie prior examples have been limited largely to those in Which there is no divalent l n f as in ous other diphenols which can be readily converted to a case at diphenyl compounds, or where the hnknig radlcal suitable polyepoxide, and particularly diepoxide, reactant. 1S 'deflved from a ketone aldehyde, Particularly a As previouslypointed out the initial phenol may be ketone. Needless tosay, the-same procedure is employed substituted, and the substituent group in turn may be va 15 cyclic group such as the phenyl group or cyclohexyl group as in the instance of cyclohexylphenol or phenylphenol. Such substituents are usually in the ortho position and may be illustrated by a phenol of the following composition:

O (B I HO (1H3 Similar phenols which are monofunctional, for instance, paraphenyl phenol or paracyclohexyl phenol with an additional substituent in the ortho position, may be employed in reactions previously referred to, for instance, with formaldehyde or sulfur chlorides to give comparable phenolic compounds having 2 hydroxyls and suitable for subsequent reaction with epichlorohydrin, etc.

Other examples include:

wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups, and wherein said alkyl group contains at least 3 carbon atoms. See U. S. Patent No. 2,515,907.

in which the -C H groups are secondary amyl groups. See U. S. Patent No. 2,504,064.

CeHia GsHra HO OH See U. S. Patent No. 2,285,563.

H CH -(B-CHs Clix-C 2 See U. S. Patent No. 2,503,196.

wherein R is a member of the group consisting of alkyl, and. alkoxy-alkyl radicals containing from 1 to 5 carbon atoms, inclusive, and aryl and chloraryl radicals of the benzene series. See U. S. Patent No. 2,526,545.

OH OH .7 I R1- (I) 7 R1 I Ha CH3 wherein R is a substituent selected from the class consisting of secondary butyl and tertiary butyl groups and R is a substituent selected from the class consisting of alkyl, cycloalkyl, aryl, aralkyl, and alkaryl groups. .See U. S. Patent No. 2,515,906.

- See U. S. Patent No. 2,515,908.

As to sulfides, the following compound is of interest:

(IJs u CsHn H OH I V See U. S. Patent No. 2,331,448."

As to descriptions of various suitable phenol sulfides, reference is made to the following patents: U. S. Patents Nos. 2,246,321, 2,207,719, 2,174,248, 2,139,766,: 2,244,-

021, and 2,195,539.

As to sulfones, see U. S. Patent No. 2,122,958. As to suitable compounds obtained by the use 'of formaldehyde or some other aldehyde, particularly comi the disulfides, and the polysulfides.

pounds such as Alkyl Alkyl Alkyl R Alkyl in which R is, amethylene radical, or a substituted methylene radical which represents the residue of an alde- CHa 011! Q in which R, and R are alkyl groups, the sum of whose carbon atoms equals 6 to about 20, and R and R each preferably contain 3 to about 10 carbon atoms, and x is 1 to 4. The term sulfides as used in this text, therefore, includes monosulfide, disulfide, and polysulfides.

PART 4 It is Well known that one can readily purchase on the open market, or prepare, fusible, organic solvent-soluble,

1 7 water-insoluble resinpolymers of a composition approximated in an idealized form by the formula OH OH OH H r H1 C C- H H R R R In the above formula 12 represents a small whole number varying from 1 to. 6, 7 or 8, or more, up to probably or 12 units, particularly when the resin is subjected to heating under a vacuum as described in the literature. A limited sub-genus is in the instance of low molecular weight polymers where the total number of phenol nuclei varies from 3 to 6, i. e., it varies from 1 to 4; R represents an aliphatic hydrocarbon substitutent, generally an alkyl radical having from 4 to carbon atoms, such as a butyl, amyl, hexy-l, decyl or dodecyl, radical. Where the divalent bridge radical is shown as being derived from formaldehyde it may, of course, be derived from any other reactive aldehyde having 8 carbon atoms or less.

Because a resin is organic so1ventsoluble does not mean it isnecessarily soluble in any organic solvent. This is particularly true where the resins are derived from trifunctional phenols as previously noted. 'However, even when obtained from a difunctional phenol, for instance paraphenylphenoh -one may obtain a resin which is not soluble in a nonoxygenated solvent, such as benzene, or xylene, but requires an oxygenated solvent such as a low molal alcohol, dioxane, or 'diethyleneglycol diethylether. Sometimes a mixture of the two solvents (oxygenated and non-oxygenated) will serve. See Example 9a of U. S. Patent No. 2,499,365, datedlvlarch 7, 1950, to De Groote and Keiser. I

The resins herein employed as raw materials must be soluble in a nonoxygenated solvent, such as benzene or xylene. This presents no problem insofar that all that is required is to make a solubility test on commercially available resins, or else prepare resins which are xylene or benzene-soluble as described in aforementioned U. S. Patent No. 2,499,365, or in U. S. Patent No. 2,499,368,

dated March 7, 1950, to De Groote and Keiser. In said patent there are described oxyalkylation-susceptible, fusible, nonoxygenated organic solvent-soluble, water insoluble, low-stage phenol-aldehyde resins having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule. These resins are difunctional only in regard to methylol-forming reactivity, are being derived by reaction between a difunctional monohydric phenol and an aldehyde having, not over 8 carbon atoms and reactive toward said phenol and are formed in the substantial absence of trifunctional phenols. The phenol is of the formula The basic nonhydroxylated amine may be designed thus:

In conducting reactions of this kind one does not necessarily obtain a hundred percent yield for obvious reasons. Certain side reactions may take place. For instance, 2 moles of amine may combine with one mole of the aldehyde, or only one mole of the amine may combine with the resin molecule, or even to a very slight extent, if at all, Z'resin units may combine without any amine in the reaction product, as indicated in the following As has been pointed out previously, as far asthe resin unit goes one can use a mole of aldehyde other than formaldehyde, such as acetaldehyde, propionaldehyde or butyraldehyde. The resin unit may be exemplified thus:

R R R in which R' is the divalent radical obtained from the particlular aldehyde employed to form the resin. For reasons which are obvious the condensation product obtained appears to be described best in terms of the method of manufacture. 1

As previously stated the preparation of resins, the kind herein employed as reactants, is well known. See previously mentioned U. S. Patent 2,499,368. Resins can be made using an acid catalyst or basic catalyst or a, catalyst having neither iacid nor basic properties in the ordinary sense or without any catalyst at all. It is preferablethat the resins employed be substantially neutral. In other words, if prepared by using a strong acid as a catalyst, such strong :acid should be neutralized. Similarly, if va strong base is used as a catalyst it is preferable that the base be neutralized although we have found that somev times the reaction described proceeded more rapidly in the presence of a small amount of a free base. The amount,

may be as small as a 200th of a percent and as much as a few 10ths of a percent. Sometimes moderate increase in caustic soda and caustic potash may be used. However, the most desirable procedure in practically every case is to have the resin neutral.

In preparing resins one does not get a single polymer,"

i. e., one having just 3 units, or just4 units, or just 5 units, or just 6 units, etc. It'is usually a mixture; for instance, one approximating 4 phenolic nuclei will have some trimer and pentamer present. Thus, the molecular weight may be suchthat it corresponds to a fractional value for n as, for example, 3.5, 4.5 or 5.2.

"19 :Ill the actual manufacture of the resins'we found no reason for using other than those which'are lowest in price and most readily available commercially. For purposes of convenience suitable resins are characterized in the following table: 7 I

- TABLE III Mol. wt Ex- Position R of resin ample R of R derived as molecule number from- (based on n+2) 1a-.-. Phenyl. Para.. Formal: 3.5 992.5

' dehyde V 2c Tertiary butyl do do 3.5 882.5 30 Secondary butyl.. Ortho. do 3.5 882.5 40 Cyclohexyl Para. ..do 3. 5 1, 025. 5 5a Tertiary amyl do-.. o 3.5 950.5 6:: Mixed secondary 7 3.5 805. 5

and tertiary amyl. 7m 3.5 805. 5 3. 5 1,030. 5 ,3. 5 1, 190. 5 3. 5 1,267.5 5. 5 1,344.5 Dodecyl 3. 5 1, 498. 5 Tertiary buty1 h d 3. 5 045. 5 y e Tertiary amyl o 3.5 1, 022.5 Non do 3.5 1,330.5 Tertiary butyl Butyral 3. 5 1,071. 5

dehyde Tertiary amyl .do 3. 5 1, 148. 5 .do. as 1, 450.5 Propional- 3. 5 1, 008. 5

dehyde. 3. 1,085.5 3.5 1,393. 5 4. 2 990. 6

4. 2 1,083.4 4. 2 l, 130. 6 Tertiary butyl 4. 8 1, 094. 4 Tertiary amyL 4. 8 1, 189. 0 N 4. 8 l, 570. 4 1. 5 604. 0 1. 5 046. 0 1. 5 653.0 1. 5 588.0

2.0 692.0 y -do 2.0 748.0 Cyclohexyl. -do. 2.0 740.0

PART 5 The expression cyclic amidines is employedin its usual sense to indicate ring compounds in which there are present either 5 members or 6 members, and having 2 nitrogen atoms separated by a single carbon atom supplemented by either two additional carbon atoms or three additional carbon atoms completing the ring. All the carbon atoms maybe substituted. The nitrogen atom of the ring involving two monovalent linkages may be substituted. --Needless 'to say, these compounds include members in which the substituents alsomay have one or more nitrogen atoms, either in the form of amino nitrogen atoms or in the form of acylated nitrogen atoms.

These cyclic amidines are sometimes characterized as being substituted imidazolines and tetrahydropyrimidines in which the two-position carbon of the ring is generally bonded to a hydrocarbon radical or comparable radical derived from an acid, suchas a low molal fatty acid, a high molal fattyacid, or comparable acids such as polycarboxy acids.

.Cyclic amidines obtained from oxidized wax acids are described in detail in co-pending Blair application, Serial No. 274,075, filed February 28, 1952. Instead of being derived from oxidized wax acids, the cyclic compounds herein employed maybe obtained from any acid-from acetic acid upward, and may be obtained from acids, s uch' as benzoic, of acids in-which there is a reoccurring ether linkage in the acyl radical. In essence then, with this difierence said aforementioned co-pending Blair application, Serial No. 274,075, describes compoundsof the following structure:

where R is a member of the class consisting of hydrocarbon radicals having up to approximately carbon atoms and includes hydroxylated hydrocarbon radicals and also hydrocarbon radicalsin which the carbon atom chain is interrupted by oxygen; n is the numeral 2 to 3, D is a member of the class consisting of hydrogen and organic radicals containing less than 25 carbon atoms, composed of the elements from the group consisting of C, N,'O andH,ai1d B is a member of the group consisting of hydrogen and hydrocarbon radicals containing less than 7 carbon atoms, with the proviso that at least three occurrences of B are hydrogen. j

The preparation. of an imidazoline substituted in the two-position by lower aliphatic hydrocarbon radicals is describedin the literature and is readily carried out by reaction between a monocarboxylic acid or ester or amide and a diamine or polyamine, containing at least one primary amino group, and at least one secondary amino group or a second primary amino group separated from the first primary amino group by two carbon atoms.

lit)

out by heating the reactants to a temperature of 230 C Examples of suitable polyamines which can be employed as reactants to form basic nitrogen-containing compounds of the present invention include polyalkylene polyamines such as ethylene-diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and higher polyethylene polyamines, and also including 1,2-

diaminopropane, N-ethylethylenediamine, N,N'-dibutyl-' diethylenetriamine, 1,2-diaminobutane, hydroxye'thylethylenediamine, 1,2 propylenetriamine', and the-like.-

For details of the preparation of imidazolines substituted in the 2-position from amines of this type, see the following U. S. Patents: U. S. No. 1,999,989, dated April 30, 1935, Max Bockmuhl et al.; U. S. No. 2,155,877, dated April 25, 1939, Edmund Waldmann. et-al.; and U. S. No. 2,155,878, dated April'25, ,1939,' .'Edmund Waldmann etal. Also see Chem. K n/ 32,47 (43).

Equally suitable for use in preparing compounds of our invention and for the preparation of -tetrahydropyrimidines substituted in the 2-position are the polyamines containing at least one primary amino group and at least one secondary amino group, or another primary amino group separated from the first primary amino group by threecarbon atoms. This reaction is generally carried or higher, usually within the range of 250 C. to 300 C., at which temperatures water is evolved and ring closure is efiected. For details of the preparation of 'tetrahydropyrimidines, see German Patent No. 700,371, dated December 18, 1940, to Edmund Waldmann and August Chwala; Gerinan'Patent No. 701,322, dated January. 14, 1941, to Karl Miescher, Ernst Erech and Willi Klarer; and U. S. Patent No. 2,194,419, dated March 19, 1940, to August .Chwala. 1 a

Examples of amines-suitable for this synthesis include 1,3-propy1ene diamine, trimethylenediamine, l,3-diaminobutane, 2,4-diaminopentane, N ethyl trimethylenediamine, N-aminoeth'yltrimethylene diamine, aminopropyl stearylamine, tripropylenetetramine, tetrapropylenepentamine, high boiling polyamines prepared by the condensation of 1,3-propylene dichloride with ammonia, and similar diamines or polyamines in which there occurs at least one primary amino group separated from another primary or secondary amino group by three carbon atoms.

Similarly, the same class of materials are included as initial reactants in co-pending Smith application, Serial No. 281,645, filed April 10, 1952.. Said .application inessence states that the cyclic compounds. employed .maybe derived from either polyamines in which thenitrogen atoms are separated by an ethylene radical'or by a trimethylene radical. Reference to a propylene radical means a methyl substituted ethylene radical, i. e., having only 2 carbon atoms between nitrogen atoms. From a practical standpoint, as will be explained hereinafter, the polyethylene imidazolines are most readily available and most economical for use. Thus, broadly speaking, using the same terminology as said Smith application, Serial No. 281,645, the present invention is concerned with a condensation reaction, in which one class of reactants are substituted ring compounds in which R is a divalent alkylene radical of the class of and in which D represents adivalent, non-amino, organic radical containing less than 25 carbon atoms, composed of elements including C, H, O, and N; Y represents a divalent, organic radical containing less than 25 carbon atoms, composed of elements includingC, H, O, and N, and containing at least one amino group, and R includes hydrogen, aliphatic hydrocarbon radicals, hydroxylated aliphatic hydrocarbon radicals, cycloaliphatic hydrocarbon radicals, and hydroxylated cycloaliphatic hydrocarbon radicals; R" includes hydrogen, aliphatic radicals and cycloaliphatic radicals, with the proviso that in the occurrence of the radicals R and R" there be present at least one group of 8 to 32 uninterrupted carbon atoms. In the present instance, however, there is no limitation in regard to the radicals R and R". a

What has been said previously in regard to the two above co-pending applications as far as substituted imidazolines are concerned is substantially the same as appears in Blair and Gross Reissue Patent No. 23,227, reissued May 9, 1950, and Monson Patent No. 2,589,198, dated April 11, 1952.

As to the six-membered ring compounds generally referred to as substituted pyrimidines, and more particularly as substituted tetra-hydropyrimidines, see US. Patent No. 2,534,828 dated December 19, 1950, to Mitchell et al. With the modification as far as the instant application goes, the hydrocarbon group R may have the same variation as when it is part of thefive-membered ring previously referred to and is not limited to an alkyl group having at least 10 carbon atoms as in the instance of the aforementioned U. S. Patent No. 2,534,828.

For the purpose of the present invention there is selected from the broad case of compounds previously described such members as meet the following limitations; (a) Have present at least one basic secondary amino radical; and (b) be free from primary amino groups and especially basic primary amino groups. Such compounds may have two-ring membered radicals present instead of one ring-membered radical and may or may not have present a tertiary amine radical or a hydroxyl radical, such as a hydroxy alkyl radical. A large number of compounds have been described in the literature meeting the above specifications, of which quite. a

few appear in the aforeme itioned issued U. S. patents. :Examples selected from the patents include the followmg:

%NO Ht v OuHn. O

Z-undecylimidazoline N-CH2 Cn as- N- C H;

2-heptadecy1imidazol1ne N- C H} CnHsaC NC H:

2-oleylimidazo1lne V NCH2 CaHa. C

CQHLNH. CwHat l-N-decylaminoethyl, 2-ethylimidazo11ne N-- O H:

C Hz G NCH2 2H4.NH.C2H4.NH. CmHas 2-met11yl, l-hexadecylaminoethylaminoethylimidazoline N-TH l I C H:

O H .NH.C12Haa 1-dodecylaminopropylimidazoline %N 0 H2 H. C

\N C H2 (IHHLNBQCZBQO 0110171135 1- (stearoyloxyethyl) aminoethylimidazoline N C H: H. C

\N C H:

1H4.NH. CzHtNHO C 0111- 1-stearamidoethylaminoethylimidazoline CzH4.N.CzH4.NHO C .OHs

1-(N-dodecyl)-acetamidoethylaminoethylimidazoline %NC H-O Ha C17H35"G N O HC Ha Z-heptadecyl, 4,5-dimethy1imidazoline N-C Ha H41 NC H2 aHmNflflnHzs I I-dodecylamlnohexylimidazollne f moi l V CdHlI-NH-CflHl. 0 (Julia: 1-stearoyloxyethylaminohexylimldaxoline N-OH:

On sr-C v /CH:

N-CH:

Jr-methyl, 2-dodecy1, 1-methylamlnoethylaminoethyl tetrahydropyrimidine As has been pointed out previously, the reactants herein employed may have two substituted imidazoline rings or two substituted tetrahydropyrimidine rings. Such compounds are illustrated by the following formula:

N CH2 V N-CH). I \N-CH: \NCH9 Such compounds can be derived, of course, from triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and higher homologues. The substituents may vary depending on the source of the hydrocarbon radical, such as the lower fatty acids and higher fatty acids, a resin acid, naphthenic acid, or the like. The group introduced may or may not contain a hydroxyl radical as in the case of hydroxyacetic acid, acetic acid, ricinoleic acid, oleic acid, etc.

One advantage of a two-ring compoundresides in the fact that primary amino groups whichconstitute the terminal radicals of the parent polyamine, whether a polyethylene amine or polypropylene amine, are converted so as to eliminate the presence of such primary amino radicals Thus, the two-membered ring compound meets the previous specification in regard to the nitrogen-containing radicals.

Another procedure to form a two-membered ring compound is to use a dibasic acid. Suitable compounds are described, for example, in aforementioned U. S. Patent No. 2,194,419, dated March 19, 1940, to Chwala.

As to compounds having a tertiary amine radical, it is aisaaaba at the secondary amino obvious that one can employ derivatives of polyaminesv in which the terminal groups are unsymmetrically alkylated. Initial polyamines of this type are illustrated by. the following formula: V i

' n l n NomANmm ,,N

radical as previously pointed out. Such derivatives, provided there is more than one secondary aminoaradical present in the ring compound, may be reacted with an alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., so as to convert one or more amino nitrogen radicals into the corresponding hydroxy alkyl'radical, provided, however, that there is still a residue secondary amine group. For instance, in the preceding formula'if n represents 4 it means the ring compound would have two secondary nitrogen radicals and could be treated with a single mole of an alkylene oxide and still provide a satisfactory reactant for the herein described condensation reaction. 1

Ring compounds, such as substituted imidazolines, may be reacted with a substantial amount of alkylene oxide as noted in the preceding paragraph'and then a secondary amino group introduced by two steps; first, reaction with an ethylene imine, and second, reaction with another mole of the oxide, or with an alkylating agent such as dimethyl sulfate, benzyl chl'oride,-a low'molal ester of a sulfonic acid, an alkyl bromide, etc.

As to oxyalkylated imidazolines and a variety of suitable high molecular weight-carboxy acids which may be the source of a substituent radical, see U. S. Patent No.

2,468,180, dated April 26, 1949, to De Groote and Keiser. a

7 Other suitable means may be employed to eliminate a terminal primary amino radical. If there isadditionally abasicsecondary amino radical present then the primary amino radical can be subjected to acylation notwithstanding the fact'that the surviving amino group has no significant basicity. As a rule acylation takes place at the terminal primary amino group rather than group, thus onecan employ a compound such as i N-CH2' C1715I35C N-CH;

C H .NH.C2H4.NH 2-heptadecyl, 1-diethylenediaminoimidazoline and subject it to acylation so as to obtain, for example, acetylated 2-heptadecyl, 1-diethylenediaminoimidazoline of the following structure: a

Similarly, a compound having no basic secondary amino radical but .a basic primary amino radical can be reacted with a mole ofan .alkylene oxide, such as ethylene oxide, propylene oxide, glycide, etc., to yield a perfectlys'atisfactory'reactant for the herein described condensation procedure, ,This can be illustrated in the a lcx ingv ma n r by a o p nd su as N-CHz CHEW-O NOHQ C2H4.NH5 Z-heptadecyl, l -aminoethylimidazoline which can be reacted with a single mole of ethylene oxide, for example, to produce the hydroxy ethyl derivative of 2-heptadecyl,l-amino-ethylimidazoline, which can be illustrated by the following formula:

%N.OHz U ar-C N-CH:

C2H4OH Other reactants may be employed in connection with an initial reactant of the kind described above, to wit, 2- heptadecyl,l-amino ethylimidazoline; .for instance, reaction with an alkylene imine such as ethylene imine, propylene imine, etc. if reacted with ethylene imine the net result is to convert a primary amino radical into a secondary amino radical and also introduces a new primary amino group. If ethylene imine is employed, the net result is simply to convert Z-heptadecyLl-aminoethylimidazoline into 2-heptadecyl,l-diethylene-diaminoimidazoline. However, if propylene imine is used the net result is a compound which can be considered as being derived hypothetically from a mixed polyalkylene amine, i. e., one having both ethylene groups and a propylene group between nitrogen atoms.

A more satisfactory reactant is to employ one obtained by the reaction of epichlorohydrin on a secondary alkyl amine, such as the following compound:

If a mole of 2-heptadecyl,1 aminoethylimidazoline is reacted with 'a mole of the compound just described, to wit,

the resultant compound has a basic secondary amino group and a basic tertiary amino group. See U. S. Patent No. 2,520,093 dated August 22, 1950, to Gross.

For purpose of convenience, what has been said by direct reference is largely by way of illustration in which there is present a sizable hydrophobe group, for instance, heptadecyl groups, pentadecyl groups, octyl groups, nonyl groups, etc. i

As has been pointed out, one can obtain all these comparable derivatives from low molal acids, such as acetic, propionic, butyric, valeric, etc. Similarly, one can employ hydroxy acids such as glycolid acids, lactic acid, etc. Over and above this, one may employ acids which introduce a very distinct hydrophobe effect as, for example, acids prepared by the oxyethylation of a low molal alcohol, such as methyl, ethyl, propyl, or the like, to produce compounds of the formula R (OCH CH ),,OH

in which R is a low molal' group, such as methyl, ethyl or propyl, and n is a whole number varying from one up to 15 or 20. Such compounds can be converted into the alkoxide and then reacted with an ester of chloracetic, followed by saponification so as to yield compounds of the type R(OCH CH ),,OCH COOH in which n has its prior significance. Another procedure is to convert the compound into a halide ether such as in in which n has its prior significance, and then react such halide ether with sodium cyanide was to give the corresponding nitrile R(OCH CH ),,CN, which can be. converted into the corresponding acid, of the following composition R(OCH CH ),,COOH. Such acids can also be used to produce acyl derivatives of the kind previously described in which acetic acidis used as an acylating agent. Whathas been said above is intended to emphasize the fact that the nitrogen compounds herein employed can vary from those which are strongly hydrophobe in character and have a minimum hydrophobe property.

Examples of decreased hydrophobe character are exemplified by 2-methylimidazoline, 2-propylimidazoline, and Z-butylimidazoline, of the following structures:

H-CH:

IYICH3 H (18) /NCH5 04H. 0

III-"CH H (19) PART 6 The products obtained by the herein described processes represent cogeneric mixtures which are the result of a condensation reaction or reactions. Since the resin molecule cannot be defined satisfactorily by formula, although it may be so illustrated in an idealized simplification, it is difficult to actually depict the final product of the cogeneric mixture except in terms of the process itself.

Previous reference has been made to the fact that the procedure herein employed is'comparable, in a general way, to that which corresponds to somewhat similar derivatives made either from phenols as differentiated from a resin, or in the manufacture of a phenol-aminealdehyde resin; or else from a particularly selected resin and an amine and formaldehyde in the manner described in Bruson Patent No. 2,031,557, in order to obtain a heatreactive resin. Since the condensation products obtained are not heat-convertible and since manufacture is not restricted to a single phase system, and since temperatures up to C. orthereabouts may be employed, it is obvious that the procedure becomes comparatively simple.

. 27 t Indeed, perhaps no description is necessary over and above what has been said previously, in light of subsequent examples. However, for purpose of clarity the following details are included.

A convenient piece of equipment for preparation of these cogeneric mixtures is a resin pot of the kind described in aforementioned U. S. Patent No. 2,499,368. In most instances the resin selected is not apt .to be a fusible liquid at the early or low temperature'stage of reaction if employed as subsequently described; in fact, usually it is apt to be a solid at distinctly higher temperatures, for instance, ordinary roomtemperature. Thus, We have found it convenient to use a solvent and par ticularly 'one which can be removed readily at a comparatively moderate temperature, for instance, at iSG" C. A suitable solvent is usually benzene, xylene, or a comparable petroleum hydrocarbon or a mixture of such or similar solvents. Indeed, resins which are not soluble except in oxygenated solvents or mixtures containing such solvents are not here included as raw materials. The reaction can beconducted insuch a way that the initial reaction, and perhaps the bulk of the r eaction, takes place in a polyphase. system. However, if desirable, one can use an'oxygenated solvent such as a low-boiling alcohol, including ethyl alcohol, methyl alcohol, etc. Higher alcohols can be used or one can use a comparatively nonvolatile solvent'such as dioxa ne or the diethylether of ethyleneglycol. One can also use a mixture of benzene or xylene and such oxygenated solvents. Note that the use of such oxygenated solvent is not required in the is approximately 37%, or it may be diluted down to about 30% formaldehyde. However, para-formaldehyde can be used but it is more difficult perhaps to add a solid material instead of the liquid solution and, everything else being equal, the latter is apt to be more economical. In any event, water is present as water of reaction. If the solvent is completely removed at the end of the process, no problem is involved if the material is used for any subsequent reaction, However, if the reaction mass is going to be subjected to some further reaction where the solvent may be objectionable, as in the case of ethyl or hexyl alcohol, and if there'is to be subsequent oxyalkylation, then, obviously, the alcohol should not be used or else it should be removed. The fact that an oxygenated solvent neednot be employed, of course, is an advantage for reasons stated.

Another factor, as far as the selection of solvent goes, is Whether or not the cogeneric mixture obtained at the end of the reaction is to be used as such or in the salt ell) form. The cogeneric mixtures obtained are apt to be solids or thick viscous liquids in which there is some change from the initial resin itself, particularly if some may be hard, resinous and comparable to the resin itself.

The products obtained, depending on the reactants selected, may be water'insoluble or water-dispersible, or water-soluble, or close to being water-soluble. Water solubility is enhanced, of course, by making a solution in the acidified vehicle such as a dilute solution, for in- 28 stance, a 5% solution of hydrochloric acid, acetic acid, hydroxyacetic acid,'etc. One also may convert the finished product into salts by simply adding a stoichiometric amount of any selected acid and removing any water present by refluxing with benzene or the like. In fact, the selection of the solvent employed may depend in part whether or not the product at the completion of the reaction is to be converted into a salt form.

In the next succeeding paragraph it js pointed out that frequently it is convenient to eliminate all solvent, using a temperatureof. not over 150 C. and employing vacuum, if required. This applies, of course, only to those circumstances where it is desirable or necessary to remove the solvent. Petroleum solvents, aromatic solvents, etc., can be used. The selection of solvent, such as benzene, xylene, or the like, depends primarily oncost, i. e., the

use of the most economical solvent and also on three.

other factors, two of which have been previously men tioned; (a) is the solvent to remain in the reaction mass without removalZ; (b) is the reaction mass to be subjected to further reaction in which the solvent, for instance, an alcohol, either, low boiling or high boiling, might interfere as in the ease of oxyalkylationZ; and the third factor is this, (o is an eflort to be made to purify the reaction mass by the usual procedure as, for example, a water-wash to remove the water-soluble unreacted formaldehyde, if any, or a water-wash to remove any unreacted Water-soluble polyamine, if employed and'present after reaction? Such procedures are well known and, needless to say, certainasolvents are more suitable than others. Everything else being equal, we have found xylene the most satisfactory solvent 7 We have found no particular. advantage in using a lowtemperature in the early stage of the reaction because, and for reasons explained, this is not necessary although it does apply in some. other procedures that, in a gem eral way, bear some similarity to the presentprocedurek There is no objection, of course, to giving the reaction an opportunity to proceed as far as it will at somelow temperature, for instance, 30 to 40 but ultimatelyone' must employ the higher temperature in order to obtain. products of the kind herein described. If a lower temperature reaction is used initially the'period is not critical, in'fact, it may be anything from a few hours up to'24 hours. We have not found any case where it was necessary or even desirable to hold the low temperature stage for more than 24 hours. In fact, we are not convinced there is any advantage in holding it at this stage for more than 3 m4 hours at the most. This, again, is a matter of convenience largely for one reason. In heating and stirring the reaction mass there is a tendency for-formaldehyde to be lost. Thus, if the reaction can be con ducted at a lower. temperature so as to use up part of, the formaldehyde at such lower temperature, then the amount of unreacted formaldehyde is decreased subsequently and makes it easier to prevent any loss. Here, again, this lower temperature is not necessary by virtue of heat convertibility as previously referred to.

If solvents and reactants are selected so the reactants and products of reaction are mutually soluble, then agitation is required only. to the extent that it helps cooling or helps distribution of the incoming formaldehyde. This mutual solubility is not necessary as previously pointed out but may be convenient under certain circumstances. On the other hand, if the products are not mutually soluble then agitation should be more vigorous'for the reason that reaction probably'takes place principally at the interfaces'and the more vigorous the agitation the more interfacial area. The general procedure employed is invariably the same when adding the resin and the selected the resin is prepared as such it may be added in solution form, just as preparation is described in aforementioned U. S. Patent 2,499,368. After the resin is in complete solution the polyamine is added and stirred. Depending on the polyamine selected, it may or may not be soluble in the resin solution. If it is not soluble in the resin solution it may be soluble in the aqueous formaldehydesolution. If so, the resin then will dissolve in the formaldehyde solution as added, and if not, it is even possible that the initial reaction mass could be a three-phase system instead of a two-phase system although this would be extremely unusual. This solution, or mechanical mixture, if not completely soluble is cooled to at least the reaction tempeature or somewhat below, for example 35 C. or slightly lower, provided this initial low temperature stage is employed. The formaldehyde is then added in a suitable form. For reasons pointed out we prefer to use a solution and whether to use a commercial 37% concentration is simply a matter of choice. In large scale manufacturing there may besome advantage in using a 30% solution of formaldehyde but apparently this is not true on a small laboratory scale or pilot plant scale. 30% formaldehyde may tend to decrease any formaldehyde loss or make it easier to control unreacted formaldehyde loss.

On a large scale if there is any difficulty with formaldehyde loss control, one can use a more dilute form of formaldehyde, for instance, a 30% solution. The reaction can be conducted in an autoclave and no attempt made to remove water until the reaction is over. Generally speaking, such a procedure is much less satisfactory for a number of reasons. For example, the reaction does not seem to go to completion, foaming takes place, and other mechanical or chemical difliculties are involved. We have found no advantage in using solid formaldehyde because even here water of reaction is formed.

Returning again to the preferred method of reaction and particularly from the standpointof laboratory procedure employing a glass resin pot, when the reaction has proceeded as one can reasonably expect at a low temperature, for instance, after holding the reaction mass with or without stirring, depending on whether or not it is homogeneous, at 30 or 40 C. for 4 or hours, or at the most, up to -24 hours, we then complete the reaction by raising the temperature up to 150 C., or thereabouts as required. The initial low temperature procedure can be eliminated or reduced to merely the shortest period of time which avoids loss of polyamine or formaldehyde. At a higher temperature we use a phase-separating trap and subject the mixture to reflux condensation until the water of reaction and the water of solution of the formaldehyde is eliminated. We then permit the temperature to rise to somewhere about 100 C., and generally slightly above 100 C., and below 150 C. by eliminating thesolvent or part of the solvent so the reaction mass stays within this predetermined range.

This period of heating and refluxing, after the water is eliminated, is continued until the reaction mass is homo geneous and then for one to three hours longer. The removal of the solvents is conducted in a conventional manner in the same way as the removal of solvents in resin manufacture as described in aforementioned U. S. Patent No. 2,499,368.

Needless to say, as far as the ratio of reactants goes we have invariably employed approximately one mole of the resin based on the molecular weight of the resin molecule, 2 moles of the secondary polyamineand 2 moles of formaldehyde. In some instances we have added a. trace of caustic as an added catalyst but have found no particular advantage in this. In other cases we have used a slight excesses of formaldehyde and, again, have not found any particular advantage in this. In other cases we have used a slight excess of nitrogen com-- pound, and, again, have not found any particular advantage in so doing. Whenever feasible We have checked the completeness of reaction in the usual ways, including the amount of water of reaction, molecular weight,

3% and particularly in some instances have checked whether or not the end-product showed surface-activity, particularly in a dilute acetic acid solution. The nitrogen content after removal of unreacted polyamine, if any is present, is another index.

In light of what has been said previously, little more need be said as to the actual procedure employed for the preparation of the herein described condensation products. The following example will serve by way of illustration:

Example 1b The phenol-aldehyde resin is the one that has been identified previously as Example 2a. It was obtained from a para-tertiary butylphenol and formaldehyde. The resin was prepared using an acid catalyst which was com letely neutralized at the end of the reaction. The molecular weight of the resin was 882.5. This corresponded to an average of about 3 /2 phenolic nuclei, as g the value for n which excludes the 2 external nuclei, i, e.,

the resin Was largely a mixture having 3 nuclei and 4 nuclei excluding the 2 external nuclei, or 5 and 6 overall nuclei. The resin so obtained in a neutral state had a light amber color.

882 grams of the resin identified as 2a, preceding, were powdered and mixed with a somewhat lesser amount of xylene, i. e., 600 grams. The mixture was refluxed until solution was complete. It was then adjusted to approximately 35 C. and 612 grams of Z-oleylimidazoline, previously shown in a structural formula as ring compound (3), were added. The mixture was stirred vigorously and formaldehyde added slowly. In this particular case the formaldehyde used was a 37% solution and 162 grams were added in approximately 3 hours. The mixture was stirred vigorously and kept within a range of approximately 40 to 44 C., for about 16 /2 hours. At the end of this time it was refluxed, using a phase-separating trap and a small amount of aqueous distillate withdrawn from time to time. The presence of unreacted formaldehyde was noted. Any unreacted formaldehyde seemed to disappear in approximately three hours after refluxing started. As soon as the odor of formaldehyde was no longer detectible the phase-separating trap was set so as to eliminate all the water of solution and reaction. After the water was eliminated part of the xylene was removed until the temperature reached approximately 148 C. The mass was kept at this higher temperature for 3 or 4 hours. During this time any additional water, which was probably water of reaction which had formed, was eliminated by means of the trap. The residual xylene was permitted to stay in the cogeneric mixture. A small amount of the sample was heated on a water bath to remove the excess xylene. The residual material was dark red in color and had the consistency of a thick sticky fluid or tacky resin. The overall reaction time was approximately 30 hours. In other examples it varied from as little as 24 hours up to approximately 38 hours. The time can. be reduced by cutting the low temperature period to approximately 3 to 6 hours. Note that in Table IV following there are a large number of added examples illustrating the same procedure. In each case the initial mixture was stirred and held at a fairly low temperature (30 to 40 C.) for aperiod of several hours. Then refluxing was employed until the odor of formaldehyde disappeared. After the odor of formaldehyde disappeared the phase-separating trap was employed to separate out all the water, both the solution and condensation. After all the water had been separated, enough xylene was taken out to have the final product reflux for several hours somewhere in the range of to 150 C., or thereabouts. Usually the mixture yielded a clear solution by the time the bulk of the water, or all of the water, had

. been removed.

in an inert solvent, i. e., one that is not oxyalkylationsusceptible. Generallyspeaking, this is most conveniently TABLE IV Amt. of Strength of Reac- Reac- Mex.

Ex. Resin Amt., Amine used amine, formaldehyde Solvent used tion tion distill.

N0. used grs. grams soln. and and amt. temp., time temp.,

, amt. 0. (hrs.) C.

612 37%, 162 g Xylene, 600 g 20-25 30 148 306 37%, 81 g.... Xylene, 450 g 21-23 24 145 306 do Xylene, 600 at... 20-22 28 150 281 30%, 100 g... Xylene, 400 g 22-24 28 148 281 .do Xylene, 450 g 21-23 30 148 281 37%, 81 g-.. Xylene, 600 g 21-25 26 146 394 do Xylene, 400 g. 23-28 V 26 147 Xylene. 450 gr--. 22-26 26 146 Xylene, 600 g 21-25 38 150 Xylene, 450 g 20-24 36 149 Xylene, 500 g. 21-22 24 142 Xylene, 650 g 20-21 26 145 Xylene, 425 g- 22-28 28 146 Xylene, 450 at 23-30 27v 150 Xylene, 550 20-24 29 147 Xylene, 440 g- 20-21 30 148 Xylene, 480 g 21-26 32 146 Xylene, 600 g 21-23 26 147 113 Xylene, 500 g 21-32 29 150 113 cd do 21-30 32 150 113 do Xylene, 550 g 21-23 37 150 126 (l0 Xylene, 440 g -22 150 126 do Xylene, 600 g 20-25 36 149 126 30%, 50 g Xylene, 400 g 20-24 32 152 7 PART 7 The products obtained as herein described by reactions involving amine condensation and diglycidyl ethers or the equivalent are valuable for use as such. This is pointed out in detail elsewhere. However, in many instances the derivatives obtained by oxyalkylation are even more valuable and from such standpoint the herein dc scribed products may be considered as valuable intermediates. Subsequent oxyalkylation involves the use of ethylene oxide, propylene oxide, butylene oxide, glycide, etc. Such oxyalkylating agents are monoepoxides as differentiated from polyepoxides.

It becomes apparent that if the product obtained is to be treated subsequently with a monoepoxide which may require a pressure vessel as in the case of ethylene oxide, it'is convenient to use the same reaction vessel in both instances. In other words, the 2 moles of the amineinodified phenol-aldehyde resin condensate would be reacted with a polyepoxide and then subsequently with a monoep'oxide. In any event, if desired the polyepoxide reaction can be conducted in an ordinary reaction vessel, such as the, usual glass laboratory equipment. This is particularly true of the kind used'for resin manufacture as described in a number of patents, as for example, U. S. Patent No. 2,499,365.

.Cognizance should be taken of one particular feature in connection with the reaction involving the polyepoxide and that is this; the amine-modified phenol-aldehyde resin condensate is invariably basic and thus one need not add the usual catalysts. which are used to promote such reactions. Generally speaking, the reaction will proceed at a satisfactory rate; under suitable conditions without any catalyst at all.

Employing polyepoxides in combination with a nonbasic reactantthe' usual catalysts include alkaline materials such as caustic soda, caustic potash, sodium methylate, 'etc. Other catalysts may be acidic in nature and are of the kind characterized by iron and tin chloride. Furthermore, insoluble catalysts such as clays or specially prepared mineral catalysts have been used. if for any reason the reaction did not proceed rapidly enough with the diglycidyl ether or other-analogous reactant, then a small amount of finely divided caustic soda or sodium methylate could be employed as a catalyst. The amount generally employed would be 1% or 2%.

It goes without saying that the reaction can take place an aromatic solvent such as Xylene or a higher boiling coal tar solvent, or else a similar high boiling aromatic solvent obtained from petroleum. One can employ an oxygenated solvent such as the diethylether of ethylene glycol, or the diethylether of propylene glycol, or similar ethers, either alone or in combination with a hydrocarbon solvent. The selection of the solvent depends in part on the subsequent use of the derivatives or reaction products. If the reaction products are tobe rendered solvent-free and it is necessary that the solvent be readily removed as, for example, by the use of vacuum distillation, thus xylene or an aromatic petroleum Will serve. it the product is going to be subjected to oxyalkylation subsequently, then the solvent should be one. whichis not oxyalkylation-susceptible. It is easyenough to select a suitable solvent if required in any instancebut everything 'else being equal, the solvent chosenshouldbethe most economical one.

Example 10 The product .was obtained by reaction between the diepoxide previously designated as diepoxide 3A, and condensate 2b. Condensate 2b was obtained fromresin 5a; resin 5a was obtained from tertiary amylphenol and formaldehyde, Condensate 2b employed as reactants resin 5a and amine 3, referred to in Table IV preceding, and more specifically the compound 2-oleylimidazoline. The amount of resin employed was 480 grams, 1 the amount of Z-oleylimidazoline employed was 306 grams, thearnount of 37%. formaldehyde employed was '81 grams, andthe amount of solvent employed was 450 grams. ,All this has been described previously.

The solution of the condensate in xylene was adjusted to a 50% solution. In this particular instance, and in practically all the others which appear in a subsequent table, the examples are characterized by the factthat no alkaline catalyst was-added. The reasonis, of course, that the condensate as such is strongly basic. If desired, a small amount of alkaline catalyst could be added, such as finely powdered caustic soda, sodium methylate, etc; if such alkaline catalyst is added it may speed up the reaction but it also may cause an undesirable reaction, such as the polymerization of the diepoxide. f I

In any event, grams of the condensate dissolved in approximately an equal weight of xylene were stirred and heated to slightly above the boiling point of water.

17 grams of the-diepoxide previously identifiedas 3A and dissolved in an equal weight of xylene were added dropwise. The initial addition of the xylene solution "carried the temperature to 'slightlyabove' the boiling point "TABLE VIII of water. The remainder of the diepoxide was added during approximately a 50 minute period. During this Probable Probable period of time the temperature rose to about 122 C. EXJNO" k gg $2 3, flgg giy The temperature was allowed to rise slightly and the 5 used product grs. grs. permoleproduct refluxed at-about 130 C. using a phase-separating trap. A small amount of xylene was removed by means of the phase-separating trap so the temperature gradually $8 g 35% rose to 150 C. and the product was refluxed at this 31940 3: 950 11980 11 temperature for about 6 hours. After this period of time 8%; Z the xylene which had been removed during the reflux 4: 770 4: 775 21390 11 period was returned to the mixture. A small amount of 828 828 258 material was withdrawn and the xylene evaporated on 'a 31040 31040 11520 12 hot plate in order to examine the physical properties. M75 590 12 The material was a dark red viscous semi-solid. It was insoluble in water, and it was insoluble in 5% gluconic At this P it y be desirable todirect'attentlon id; i was l bl i Xylene d p i l i i to itwo facts,the first being that we are aware that other m of 30% Xylene and h l However if diepoxides freefrom an aromatic radical as, for example, the material was dissolved in an oxygenated solvent and ePOXidBS derived fmm ethylene glycol: mr, The then shaken with 5% gluconic acid it showed a definite 20 llikeysuch 215 I116 following: tendency to disperse, suspend, or'forrn a sol, and vpar- H H H H H H H ticularly in a xylene-methanol mixed solvent as 'previously described, with or without the further addition of a H 0 H little acetone. o H O The procedure employed of course is simply in light of H H H H what has been said previously and in effect is a procedure HOC CCOCCH similar to that employed in the use of glycide or methyl- H H glycide as oxyalkylating agents. See, for example, Part 1 of U. .8. Patent No. 2,602,062, dated -July 1, 1952, to may be employed to replace the diepoxides herein de- De Groote. scribed; However, such derivatives are not included as Various examples obtained in substantially the same part of the instant invention. manner are enumerated in the following tables: At times we have found a tendency for an insoluble TABLE V Con- Diep- Time Max. Ex. den- Amt., oxide Amt, Xylene, Molar of reactemp., Color and physical state No. sate grs. used grs. grs. ratio tion, 1 0.

used hrs.

160 3A 17 177 2:1 8 Dark solid mass. 3A 17 172 2:1 7 155 D0. 169 3A 17 186 2:1 3 158 Do 177 3A 17 194 2:1 8 155 Do 173 3A 17 190 2: 1 8 D0 211 3A 17 228 2:1 3 152 Do. 170 3A 17 137 21 8 158 Do. 124 3A 17 141 2:1 6 160 Do. 125 3A 17 142 2:1 6 162 Do. 131 3A 17 148 2:1 6 158 D0.

TABLE VI Con- Diep- Time Max. Ex. den- Amt, oxide Amt, Xylene, Molar of reactemp., Color and physical state No. sate grs. used grs. grs. ratio tion, 0.

used V hrs.

160 B1 27. 5 188 2:1 8 155 Dark solid mass. 155 B1 27.5 183 2&1 s 160 Do. 169 B1 27.5 197 2: 1 s 162 D0 177 B1 27.5 205 2:1 8 158 Do 173 B1 27.5 200 2: 1 8 165 D0 211 B1 27.5 239 2: 1 s 156 D0 B1 27.5 198 2: 1 8 161 Do 124 B1 27.5 152 2: 1 7 164 Do 125 B1 27.5 153 2: 1 7 153 D0 131 B1 27.5 159 2: 1 7 160 Do Solubility in regard to all these compounds was substan- 50 mass to form or at least to obtain incipient cross-linking tially similar to that which was described in Example 1C. or gelling even when the molal ratio is in the order of 2 TABLE VII moles of resin to one of diepoxide. We have found this can be avoided by any one of the following procedures or Probable Pro a l their equivalent. Dilute the resin or the diepoxide, or

Ex. No. i iie t i n rii ilii jeii gir if both, with an inert solvent, such as xylene or the like. use product p g In some instances an oxygenated solvent, such as the diethyl ether of ethyleneglycol may be employed. Another procedure which is helpful is to reduce the amount of 3530 L770 catalyst used, or reduce the temperature of reaction by 3,430 3, 445 1,730 11 32 38 g3 gig adding a small amount of mtttally lower bOlllIlg solvent 3:800 3:800 :5 such as benzene, or use benzene entirely. Also, we have $28 gfound it desirable at times to use slightly less than ap- 21530 21235 11420 11 parently the theoretical amount of diepoxide,for instance 2:228 iggg 58 90% to 95% instead of 100%. The reason for'this fact 75 may reside in the possibility that the molecularweight dimensions on either the resin molecule or the diepoxide molecule may actually vary from the true molecular weight by several percent.

Previously the condensate has been depicted in a simplified form which, for convenience, may be shown thus:

. (Amine)CH (Resin)CH (Amine) 7 Following such simplification the reaction product with a polyepoxide and particularly a diepoxid, .wouldlbe indicated thus:

, [(Amine)CH (Resin)CH (Amine)] p V V D: E Ammoomutesin H.(Amine [(Amine) Q Hz(Amine) (Resin) on (Resln)] I: 2

I: (Amine) 0 Hz (Amine) All the above indicates the complexity of the reaction product obtained after treating the amine-modified resin condensate with a polyepoxide and particularly diepoxide as herein described.

PART 8 Conventional demulsifying agents employed in the treatment of oil field emulsions are used as such, or after dilution with any suitable solvent, such as Water, petroleum hydrocarbons, such as benzene, toluene, xylene, tar

acid oil, cresol, anthracene oil, etc. Alcohols, particularly aliphatic alcohols, such as methyl alcohol, ethyl alcohol, denatured alcohol, propyl alcohol, butyl alcohol, hexyl alcohol, octyl alcohol, etc., may'be employed as diluents. Miscellaneous solvents such as pine oil, carbon tetrachloride, sulfur dioxide extract obtained in the refining of petroleum, etc., may be employed as diluents.

. exhibits relatively limited oil-solubility. i-lowever, since such reagents are frequently used in a ratio of l to 10,000

or 1 to 20,000, or 1 to 30,000, or even 1 to 40,000, or

1 to 50,000 as in desalting practice, such an apparent insolubility in oil and water is not significant because said reagents undoubtedly have solubility within such concentrations. This same fact is true in regard to the material or materials of. our invention when employed as de' mulsifying agents.

The products herein -The materials of our invention, when employed as treating or demulsifying agents, are used inthe conventionalway, well known to the art, described, for example, in Patent 2,626,929, dated January 27, 1953, Part 3, and reference is made thereto for a description of conventional procedures of demulsifying, including batch, continuous, and down-the-hole demulsification, the process essentially involving introducing a small amount of demulsifier into a large amount of emulsion with adequate admixture with or without the application of heat, an

allowing the mixture to stratify. e

As noted above, the products herein described may be used not only indiluted form, but also may be used admixed with some other chemical demulsifier. A mixture which illustrates. such combination is the following:

The product of the present invention, for example, the product of Example 1C, 20%

A cyclohexylamine salt of a polypropylated' napthalene monosulfonic acid, 24%;

An ammonium salt of a polypropylated napthalene monosulfonic acid, 24%;

A sodium salt of oil-soluble mahogany petroleum sul- "fonic acid, 12%;

A high-boiling aromatic petroleum solvent, 15%;- Isopropyl alcohol, 5%. .The above proportions are all weight percents.

PART 9 described as such and prepared in accordance with this invention can be used as emulsifying agents for oils, fats and Waxes, as ingredients in insecticide compositions, or as detergents and Wetting agents in the laundering, scouring, dyeing, tanning and mordanting industries. They may also be used for preparing boring or metal-cutting oils and cattle dips, as metal pickling inhibitors, and for pharmaceutical purposes.

Other uses include thepreparation or resolution of petroleum emulsions, whether of the water-in-oil type or oil-in-Water type. They may be used as additives infconnection with other emulsifying agents; they may be employed to contribute hydrotropic effects; they may, be used as anti-strippers in connection with asphalts; they may be used to prevent corrosion, particularly the corrosion of ferrous metals for various purposes and particularly in connection with the production of oil and gas, and :also in refineries where crude oil is converted into various commercial products. The products may be used industrially to inhibit or stop micro-organic growth or other objectionable lower forms of life, such as the growth of algae, or the like; they may be used to inhibit the growth of bacteria, molds, etc.; they are valuable additives to lubricating oils, both those derived from petroleum and synthetic lubricating oils, and also to hydraulic brake fluids of the aqueous or non-aqueous type; some have definite. anti-corrosive action; used also in connection with other processes Where they are injected into an oil or gas Well for purpose of removing a mud sheath, increasing the ultimate flow of fluid from the surrounding strata, and particularly in secondary recovery operations using aqueous flood waters. They can also be used in dry cleaners soaps.

With regard to the above statements, reference is made particularly to the use of the materials as such, or in the form of a salt; the salt form refers to a salt involving either one or both basic nitrogen atoms. Obviously, the salt form involves a modification in which the hydrophile character can be either increased or decreased and,

, inversely, the hydrophobe character can be decreased or increased. For example, neutralizing the product with practically any low molal acid, such as acetic acid, bydroxyacetic acid, lactic acid, or nitric acid, is apt to markedly increase the hydrophile effect. One may also use acids of the type They may be out sludge.

ing with aqueous alcohol. -fi'rstrecovere'd as a water curd after removal of alcohol in which :is a comparatively small alkyl radical, 'such as methyl, ethyl or propyl. The hydrophile effect may be decreased and the hydrophobe efiect increased by neutralization with a monocarboxy detergent-forming acid. These are acids which have at least 8 and not more than 32 carbon atoms. They are obtained from higher fatty acids and include also resin acids such as "abietic acid, and petroleum acids such as naphthenic acids and acids obtained by the oxidation of wax. One can also obtain new products having unique properties by combination with polybasioacids, such as diglycolicac-id, oxalic acid, dimeriz'ed acids'fromlinseed oil, etc. Thernos't common examples, of course, are the higher fatty acids having generally 10 to 18 carbon atoms. We have found that 'a'particularly valuable anti-corrosive agent can be obtain'ed fromany: suitable resin'and formaldehyde provided the secondary amine is dicyclohexylamine. The corrosion-inhibiting properties of this compound can be increased by neutralization with either one or two moles of an oil-soluble sulfonic acid,'particularly a sulfonic acid of the type known as mahogany sulfonic acid.

The oil-soluble sulfonic acids previously referred to may be synthetically derived by sulfonating olefins, aliphatic 'fatty acids, or-t-heir' esters, alkylated aromatics or their hydroxyl derivatives, partially hydrogenated aromatics, -etc., with sulfuric acid or other sulfonating agents. However, 'the'soa'ps of so-called mahogany acids which are usually produced during treatment of lubrieating oil distil lates withconcentrated sulfuric acid (85% or higher c'oncentration) remainin the oil after settling These sulfonic acids may be represented as where (R),, is 'one or more alkyl, alkaryl or aralkyl groups and the aromaticnucleus may be a'single or condensed ring or a partially hydrogenated ring. The lower molecular weight acids can be extracted from the acid treated 'oil by adding a small amount of water, prefer- "ably after dilution of the oil with kerosene. However,

the more desirable high molecular weight (350-500) acids, particularly thoseproduced when treating petroleacid oil with sodium hydroxideor carbonate and extract.- .The'crude soap extract is *tained co'nverted into free acids.

Not only can one obtain by-product sulfonic acids-of the'mahogany type which are perfectly satisfactory and as the principal product of reaction and have all the usual characteristics of normal by-product sulfonic acids but in some instances contain two sulfonic groups, i. e.,

are disulfonic acids. This type of mahogany acid, or better still, oil-soluble sulfonic acid, is perfectly satisfactory for the above described purpose.

Much of what has been said previously is'concerried with derivativesin which the hydrophile properties are "enhanced in comparison with the resin as such. A procedure designed primarily to enhance the hydrophobe properties of the resin involves derivatives obtained by a phenyl or substituted phenyl glycidyl ether of the structure mWOo-crn-on-onl in which R represents a hydrocarbon substituent such as an alkyl radical having 1 to 24 carbon atoms, or a cyclic group, such as a cyclohexyl group, a phenyl group, or a benzyl group, and n represents 0, 1, 2 or 3. h is zero in the instance of the unsubstituted phenyl radical. Such compounds are in essence oxyalkylating agents and reactioninvolves the introduction of a hydrophobe group 'and thefor'ma'tion of'an alkanol hydroxyl radical.

'As far as" the us'e'ofthe herein described products goes for purpose of resolution of petroleum emulsions of the water-in-oil type, we particularly prefer to use those which as such or in theform' of-the free base or hydrate, i. e., combination of water or particularly in the form of a low molal organic acid such as the acetate or hydroxyacetate, have sulficiently hydrophile character to at least meet the-tests set' forth in U. '8. Patent No. 2,499,368,

*dated Marohfl, -1'950,toDe Grooteet al. In said patent such test EfOI' v ernulsification using a water-insoluble solvent, generally xylene, is described as an index of reaction between "a 'difunctional monohydricphenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the sub- :stantial absence of trifunctional phenols; said phenol :being of the formula in which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and within the molecular range of 300 to 600 but also one can obtain somewhat similar material which are obtained substituted tetrahydropyrimidines in which there is present at least one basic secondary amino radical and characterized .by freedom from anyprimary amino radical; and (0) formaldehyde; said condensation reaction being conducted at "a temperature-sufficiently high to eliminate water and below the pyrolytic point of thereactants and resultantsof reaction; and. with the proviso that the resinous condensation product resulting from the process be heat-stable and oxya-lkylation-susceptible; followed by (B) reacting said" resin condensate with a'phenolic polyepoxide containing at last two l,2-epoxy ringsand being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups and-cogenerically associated compounds formed in thepreparationof .said polyepoxides; said epoxides beingv monomers and low molal polymers not exceeding the tetramers; 'sai'd polyepoxides being selected from the class consisting of (an) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (M1) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehyde oxygen atom, the divalent radical radical, the divalent sulfone radical, and the divalent monosulfide radical --S, the divalent radical CH SCH V and the divalent disulfide radical S-S-; said phenolic portion of the diepoxide being obtained from a phenol of the structure the divalent I and the divalent disulfide radical SS-;'said phenolic said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the results of reaction; and with the final proviso that the ratio of reactants be approximately 2 moles of' the resin condensate per mole of the phenolic polyepoxide.

2. The method of (A) condensing (a) an oxyalklation-susceptible, fusible, non-oxygenated organic solventsoluble water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the formula in'which R is an aliphatic hydrocarbon radical having at least 4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrirnidines in whichthere is present at least one basic secondary amino radical and characterized by freedom'from any primary amino radical;

and (0) formaldehyde; said condensation reaction being conducted at a temperature sulficiently high to eliminate water and below the pyrolytic point of the reactants and resultants of reaction; and with the proviso that the resinous; condensation product resulting from the process be heat-stable and oxyalkylation-susceptible; followed by (B) reacting a phenolic diepoxide containing two 1,2- epoxy rings and being free from reactive functional groups other than 1,2-epoxy and hydroxyl groups, and cogenerically associated compounds formed in the preparation of said diepoxides; said epoxides being selected from the class consisting of (aa) compounds where the phenolic nuclei are directly joined without an intervening bridge radical, and (bb) compounds containing a radical in which 2 phenolic nuclei are joined by a divalent radical LE H:

' susceptible, 4o

selected from the class consisting of ketone residues formed by the elimination of the ketonic oxygen atom, and aldehyde residues obtained by the elimination of the aldehydic oxygen atom, the divalent radical the divalent radical, the divalent sulfone radical, and the divalent monosulfide radical S, the divalent radical CH SCH portion of the diepoxide being obtained from a phenol of the structure in which R, R", and R represent a member of the class consisting of hydrogen and hydrocarbon substituents of the aromatic nucleus, said substituent member having not over 18 carbon atoms; the molar ratio of reactant (A) to reactant (B) being approximately 2 to 1 respectively; with the further proviso that said reactive compounds (A) and (B) be members of the class consisting of non -thermosetting organic solvent-soluble liquids and low-melting solids; with the final proviso that the reaction product be a member of the class of solvent-soluble V liquids and low-melting solids; and said reaction between (A) and (B) being conducted below the pyrolytic point of the reactants and the resultants of reaction. I

3. The method of (A) condensing (a) an oxylkylationfusible, non-oxygenated organic solventsoluble, water-insoluble, low-stage phenol-aldehyde resin having an average molecular weight corresponding to at least 3 and not over 6 phenolic nuclei per resin molecule; said resin being difunctional only in regard'to methylolforming reactivity; said resin being derived by reaction between a difunctional monohydric phenol and an aldehyde having not over 8 carbon atoms and reactive toward said phenol; said resin being formed in the substantial absence of trifunctional phenols; said phenol being of the in which R is an aliphatic hydrocarbon radical having at least '4 and not more than 24 carbon atoms and substituted in the 2,4,6 position; (b) cyclic amidines selected from the class consisting of substituted imidazolines and substituted tetrahydropyrimidines in which there is prestent at least one basic secondary amino radical and charcondensation product resulting from the process be heatstable and oxyalkylation-susceptible; followed by (B) reacting a member of the class consisting of (aa) compounds of the following formula: 

1. THE METHOD OF (A) CONDENSING (A) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, NON-OXYGENATED ORGANIC SOLVENTSOLUBLE, WATER-INSOLUBLE, LOW-STAGE PHENOL-ALDEHYDE RESIN HAVING AN AVERAGE MOLECULAR WEIGHT CORRESPONDING TO AT LEAST 3 AND NOT OVER 6 PHENOLIC NUCLEI PER RESIN MOLECULE; SAID RESIN BEING DIFUNCTIONAL ONLY IN REGARD TO METHYLOL-FORMING REACTIVITY; SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 